Multifunctional interfacial layer and composite membrane and solid-state battery using the same

Abstract

Disclosed is a multifunctional interfacial layer, which includes a conducting fiber network and a polymer-based conductive medium. The conducting fiber network layer can serves as a physical barrier to contain lithium dendrites and provide mechanical strength. The polymer-based conductive medium can facilitate smooth contact with electrodes. Under thermal treatment, an interface additive included in the polymer-based conductive medium can diffuse to the surface of the electrode, resulting in formation of an in-situ interfacial layer on the electrode. Accordingly, the multifunctional interfacial layer can resolve the problems of poor mechanical property and chemical instability at elevated potential and temperature associated with PEO-succinonitrile solid polymer electrolyte and prevent dendritic growth of lithium anode.

What is claimed is: 
     
         1 . A solid-state battery, comprising:
 a first electrode;   a second electrode; and   a composite membrane sandwiched between the first electrode and the second electrode and including a first multifunctional interfacial layer and a plasticizer-containing electrolyte,   wherein the first multifunctional interfacial layer includes a first conducting fiber network and a first polymer-based conductive medium infused into porous areas of the first conducting fiber network and adjacent to the first electrode,   wherein the first polymer-based conductive medium contains a first interface additive therein and serves as a first conductive gel or the first interface additive diffuses from the first polymer-based conductive medium to form a first in-situ interfacial layer between the first electrode and the first polymer-based conductive medium, and   wherein the plasticizer-containing electrolyte is combined with the first conducting fiber network and spaced from the first electrode by the first multifunctional interfacial layer.   
     
     
         2 . The solid-state battery of  claim 1 , wherein the composite membrane further includes a second multifunctional interfacial layer, wherein:
 the second multifunctional interfacial layer includes a second conducting fiber network and a second polymer-based conductive medium infused into porous areas of the second conducting fiber network and adjacent to the second electrode,   the second polymer-based conductive medium contains a second interface additive therein and serves as a second conductive gel or the second interface additive diffuses from the second polymer-based conductive medium to form a second in-situ interfacial layer between the second electrode and the second polymer-based conductive medium, and   the plasticizer-containing electrolyte is combined with the second conducting fiber network and spaced from the second electrode by the second multifunctional interfacial layer.   
     
     
         3 . The solid-state battery of  claim 1 , wherein the first conducting fiber network includes a first conductive polymer and first stiffeners as constituents thereof. 
     
     
         4 . The solid-state battery of  claim 3 , wherein the first stiffeners are multi-walled carbon nanotubes. 
     
     
         5 . The solid-state battery of  claim 3 , wherein the first conductive polymer includes an ionic-electric dual-conductive polymer and an ionic conductive polymer. 
     
     
         6 . The solid-state battery of  claim 5 , wherein the ionic-electric dual-conductive polymer is PEDOT:PSS copolymer. 
     
     
         7 . The solid-state battery of  claim 5 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         8 . The solid-state battery of  claim 3 , wherein the first conducting fiber network further includes a first binder. 
     
     
         9 . The solid-state battery of  claim 1 , wherein the first polymer-based conductive medium includes an ionic conductive polymer and lithium salts. 
     
     
         10 . The solid-state battery of  claim 9 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         11 . The solid-state battery of  claim 1 , wherein the first in-situ interfacial layer is formed by oxidation of the first interface additive. 
     
     
         12 . The solid-state battery of  claim 1 , wherein the first interface additive is fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC) or a combination thereof. 
     
     
         13 . The solid-state battery of  claim 2 , wherein the second conducting fiber network includes a second conductive polymer and second stiffeners as constituents thereof. 
     
     
         14 . The solid-state battery of  claim 13 , wherein the second stiffeners are multi-walled carbon nanotubes. 
     
     
         15 . The solid-state battery of  claim 13 , wherein the second conductive polymer includes an ionic-electric dual-conductive polymer and an ionic conductive polymer. 
     
     
         16 . The solid-state battery of  claim 15 , wherein the ionic-electric dual-conductive polymer is PEDOT:PSS copolymer. 
     
     
         17 . The solid-state battery of  claim 15 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         18 . The solid-state battery of  claim 13 , wherein the second conducting fiber network further includes a second binder. 
     
     
         19 . The solid-state battery of  claim 2 , wherein the second polymer-based conductive medium includes an ionic conductive polymer and lithium salts. 
     
     
         20 . The solid-state battery of  claim 19 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         21 . The solid-state battery of  claim 2 , wherein the second in-situ interfacial layer is formed by oxidation of the second interface additive. 
     
     
         22 . The solid-state battery of  claim 2 , wherein the second interface additive is fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC) or a combination thereof. 
     
     
         23 . The solid-state battery of  claim 1 , wherein the plasticizer-containing electrolyte includes a solid-state electrolyte matrix and a plasticizer in the solid-state electrolyte matrix. 
     
     
         24 . The solid-state battery of  claim 23 , wherein the plasticizer is succinonitrile. 
     
     
         25 . The solid-state battery of  claim 1 , wherein the first conducting fiber network has a thickness of from 0.1 to 10 μm. 
     
     
         26 . The solid-state battery of  claim 1 , wherein the first polymer-based conductive medium has a thickness of from 0.01 to 5 μm. 
     
     
         27 . The solid-state battery of  claim 2 , wherein the second conducting fiber network has a thickness of from 0.1 to 10 μm. 
     
     
         28 . The solid-state battery of  claim 2 , wherein the second polymer-based conductive medium has a thickness of from 0.01 to 5 μm. 
     
     
         29 . A multifunctional interfacial layer, comprising:
 a conducting fiber network; and   a polymer-based conductive medium infused into porous areas of the conducting fiber network, wherein the polymer-based conductive medium contains an interface additive therein and serves as a conductive gel.   
     
     
         30 . The multifunctional interfacial layer of  claim 29 , wherein the conducting fiber network includes a conductive polymer and stiffeners as constituents thereof. 
     
     
         31 . The multifunctional interfacial layer of  claim 30 , wherein the stiffeners are multi-walled carbon nanotubes. 
     
     
         32 . The multifunctional interfacial layer of  claim 30 , wherein the conductive polymer includes an ionic-electric dual-conductive polymer and an ionic conductive polymer. 
     
     
         33 . The multifunctional interfacial layer of  claim 32 , wherein the ionic-electric dual-conductive polymer is PEDOT:PSS copolymer. 
     
     
         34 . The multifunctional interfacial layer of  claim 32 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         35 . The multifunctional interfacial layer of  claim 30 , wherein the conducting fiber network further includes a binder. 
     
     
         36 . The multifunctional interfacial layer of  claim 29 , wherein the polymer-based conductive medium includes an ionic conductive polymer and lithium salts. 
     
     
         37 . The multifunctional interfacial layer of  claim 36 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         38 . The multifunctional interfacial layer of  claim 29 , wherein the interface additive is fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC) or a combination thereof. 
     
     
         39 . A composite membrane, comprising a first multifunctional interfacial layer and a plasticizer-containing electrolyte, wherein:
 the first multifunctional interfacial layer includes a first conducting fiber network and a first polymer-based conductive medium infused into porous areas of the first conducting fiber network from a first side of the first conducting fiber network;   the plasticizer-containing electrolyte is combined with the first conducting fiber network from a second side of the first conducting fiber network opposite to the first side; and   the first polymer-based conductive medium contains a first interface additive therein and serves as a first conductive gel.   
     
     
         40 . The composite membrane of  claim 39 , further comprising a second multifunctional interfacial layer, wherein:
 the second multifunctional interfacial layer includes a second conducting fiber network and a second polymer-based conductive medium;   the plasticizer-containing electrolyte is combined with the second conducting fiber network from a first side of the second conducting fiber network; and   the second polymer-based conductive medium contains a second interface additive therein and serves as a second conductive gel infused into porous areas of the second conducting fiber network from a second side of the second conducting fiber network opposite to the first side.   
     
     
         41 . The composite membrane of  claim 39 , wherein the first conducting fiber network includes a first conductive polymer and first stiffeners as constituents thereof. 
     
     
         42 . The composite membrane of  claim 41 , wherein the first stiffeners are multi-walled carbon nanotubes. 
     
     
         43 . The composite membrane of  claim 41 , wherein the first conductive polymer includes an ionic-electric dual-conductive polymer and an ionic conductive polymer. 
     
     
         44 . The composite membrane of claim  44 , wherein the ionic-electric dual-conductive polymer is PEDOT:PSS copolymer. 
     
     
         45 . The composite membrane of  claim 44 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         46 . The composite membrane of  claim 41 , wherein the first conducting fiber network further includes a first binder. 
     
     
         47 . The composite membrane of  claim 39 , wherein the first polymer-based conductive medium includes an ionic conductive polymer and lithium salts. 
     
     
         48 . The composite membrane of  claim 47 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         49 . The composite membrane of  claim 39 , wherein the first interface additive is fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC) or a combination thereof. 
     
     
         50 . The composite membrane of  claim 40 , wherein the second conducting fiber network includes a second conductive polymer and second stiffeners as constituents thereof. 
     
     
         51 . The composite membrane of  claim 50 , wherein the second stiffeners are multi-walled carbon nanotubes. 
     
     
         52 . The composite membrane of  claim 50 , wherein the second conductive polymer includes an ionic-electric dual-conductive polymer and an ionic conductive polymer. 
     
     
         53 . The composite membrane of  claim 52 , wherein the ionic-electric dual-conductive polymer is PEDOT:PSS copolymer. 
     
     
         54 . The composite membrane of  claim 52 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         55 . The composite membrane of  claim 50 , wherein the second conducting fiber network further includes a second binder. 
     
     
         56 . The composite membrane of  claim 40 , wherein the second polymer-based conductive medium includes an ionic conductive polymer and lithium salts. 
     
     
         57 . The composite membrane of  claim 56 , wherein the ionic conductive polymer is PEO polymer, a PVDF polymer or a combination thereof. 
     
     
         58 . The composite membrane of  claim 40 , wherein the second interface additive is fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC) or a combination thereof. 
     
     
         59 . The composite membrane of  claim 39 , wherein the plasticizer-containing electrolyte includes a solid-state electrolyte matrix and a plasticizer in the solid-state electrolyte matrix. 
     
     
         60 . The composite membrane of  claim 59 , wherein the plasticizer is succinonitrile. 
     
     
         61 . The composite membrane of  claim 39 , wherein the first conducting fiber network has a thickness of from 0.1 to 10 μm. 
     
     
         62 . The composite membrane of  claim 39 , wherein the first polymer-based conductive medium has a thickness of from 0.01 to 5 μm. 
     
     
         63 . The composite membrane of  claim 40 , wherein the second conducting fiber network has a thickness of from 0.1 to 10 μm. 
     
     
         64 . The composite membrane of  claim 40 , wherein the second polymer-based conductive medium has a thickness of from 0.01 to 5 μm.